Polyamine resinous composition and an ink made therefrom



Patented Feb. is, 1949 POLYAMINE RESINOUS COMPOSITION AND AN INK MADETHEBEFBOM Frederick Edward Petke, Cincinnati, Ohio, as-

signer to Sterling Drug Inc New York, N. Y., a corporation of DelawareNo Drawing. Application August 14, 1945, Serial No. 610,879

18 Claims. (Cl. 106-30) This invention relates to coating and printingcompositions containing resinous materials, and more particularly tocompositions containing polyamine salts of acidic resins. Thesecompositions are adapted for use in coatings and are of special value inthe formulation of printing inks, although the invention is not limitedto such uses.

It has been proposed heretofore to employ various acidic resinoussubstances in coating or in printing ink compositions and some of thesehave achieved ameasure of commercial success. The value of thesecompositions, however, is limited by their inherent defects. The acidiccharacter of the resins tends to make them corrosive and thus theycannot be applied to surfaces which may be corroded thereby. When usedin printing ink vehicles, it is dimcult to disperse pigments therein,and the acidic constituents tend to decompose or otherwise destroy someof the pigment materials commonly used in ordinary printing ink. Many ofthese compositions also tend to thicken and become heavy in body andeventually even to coagulate into heavy liverlike masses.

Several proposals have been made in the effort to mitigate theseconditions. For example, in the case of printing inks, it has beenproposed that the pigment particles be coated with a neutral protectingresin which insulates the pigment itself from the corrosive action ofthe acid groups in the resin vehicle. This is expensive, and it tends tomarkedly alter the viscosity, tone and other characteristics of theresulting ink composition. In general, the proposals made heretofore forreducing the acidic character of the resin altered its solubility,viscosity or drying characteristics to such an extent as to render itundesirable for coating or printing ink usage.

Surprisingly enough, it has now been found that the foregoing objectionscan be overcome by the presence of salts of the acidic resin and certainpolyamine substances. These salt resin compositions have improvedpigment wetting properties, better viscous stability and may be socompounded as to have better solubility characteristics than the acidicresin compositions.

The objects as achieved by the present invention include the provisionof an acidic resin salt composition adapted for coating purposes; theprovision of an acidic resin salt printing ink composition containingthe usual pigments and having no corrosive action on said pigments; theprovision of ink vehicles having improved pigment wetting properties;the provision of print- 2 ing inks of high viscous stability; and otherobiects as will be apparent as the invention is more fully developedhereinafter.

In accordance with the invention, an acidic resin is treated with apolyamine and the resulting resinous composition contains a polyaminesalt of the acidic resin. The resin and the polyamlne may be so selectedthat the resulting salt resin will have desired solubilitycharacteristics in solvents such as those usually used in inkformulations. The resulting salt resin has a much superior pigmentwetting power than the original acidic resin. The polyamine salt resincompositions have excellent drying characteristics, and at the same timetheir viscous stability is, also very high; that is, they do not tend to"heavy up" or liver" in body and thus are markedly superior to theheretofore proposed acidic resinous coating or printing ink vehiclecompositions.

A wide range of acidic resins may be used in preparing the polyaminesalt resins. One type is the adduct obtained by reacting rosin with anolefin dicarboxylic acid or derivative thereof. These include therosin-maleic anhydride, rosinmaleic diester, and the rosin-maleic acidad ducts: and also the rosin-fumaric diester and rosin-iumaric acidadducts. Another type is the adduct of terpene and an olefindicarboxylic acid or derivative thereof. These may be prepared from avariety of terpenes and, for instance, either the maleic or fumaricacids or derivatives by the so-called diene syntheses. Various alkydresins having free acidic groups may be employed. These resins may beobtained by reacting a poly basic acid or anhydride with a higherpolyhydric compound; for instance, by the reaction of phthalic anhydrldewith glycerol. Substantially neutral resinous materials which can bemodifled by reaction with an olefin carboxylic acid anhydride may beused. The modification results in a product having. carboxy groups.

The polyamines oi' the ethylene diamine series have been found to beeminently suitable. Thisseries includes ethylene diamlne, diethyienetriamine, triethylene tetramine, etc. Even the higher members of thisseries are suitable; for instance, members containing 40 or moreethylene groups work satisfactorily. The substitution derivatives of thepolyethylene polyamines have also been found to be suitable. One ofthese has each amino hydrogen thereof replaced by an ethanol group.Another has each amino hydrogen replaced by an ethyl group. Another haseither one or both of the terminal NH: groups replaced by a morpholinering. Other polyamines menus that may be used include urea and polyurea,melamine, or other amino-triazine derivatives, and the fully substitutedamines including quarternary ammonium ion compounds.

The polyamine acidic resin salt is substantially amide-free and may beformed by dissolving the resin in a solvent and then adding thepolyamine; or alternatively, the amine may be dissolved inthe solventand then the resin added. In some cases, the solvent may be dispensedwith and the polyamine reacted directly with the acidic resin.- Theamount of polyamine used is sufficient to form a salt with at least someof the acid groups in the resin, but in many cases the amount used isnot enough to neutralize all the acid groups in the acidic resin.

In formulating ink oi the polyamine acidic resin salt type, the pigmentmay be ground, or merely mixed or flushed, in the solution of the saltin the solvent in which the salt is prepared, or by first forming thesalt and then dissolving it in the solvent. The pigment may beincorporated into an acidic resin by the usual grinding procedure andthen the polyamine added thereto; inks formulated with acidic resins maybe improved or stabilized in accordance with the invention by adding thepolyamine thereto.

In general, the lower molecular weight polyamines tend to impart ahigher pH increase per given weight of nitrogen and a smaller increasein tack and viscosity than do the higher molecular weight amines. Thepolyethylene polyamine salts have a lower water tolerance and theirdrying time is higher than that of the corresponding acidic resins whichare used in steamset inks. The salts of the polyethylene polyaminederivatives having all the amino hydrogens replaced by ethanol groupshave a higher water tolerance than the corresponding acidic resin usedin steam-set inks and their drying time is lower. The viscosity and tackof this resin are lower than those of the corresponding polyethylenepolyamine resin.

By using a mixture of completely substituted polyethylene polyamine andnon-substituted polyethylene polyamine. it is possible to producepolyamine resin having a desired viscosity, tack, and in the case ofsteam-set inks, water tolerance characteristics. A similar effect can beachieved by using partially substituted polyethylene polyamines havingdifferent substituents.

All of these polyamine acid resin salts have excellent pigment wettingproperties. The polyamine salt of a moisture setting ink has excellentmoisture wetting properties. Steam or a mist of water may be used.

For use in coating compositions, the polyamine salt of the acidic resinshould have molecular weight or solubility characteristics such that itis soluble in the usual ink varnish solvents, such as the poly glycolsor drying oils, and other solvents such as used in rotogravure orheat-set The improved pigment wetting. body and flow, strength of tilm,tone, and the like characteristics may be obtained in any type acidicresin containing coating or printing ink in accordance with theinvention. These include: drying oil type inks and varnishes modifiedwith polybasic acid resins; rotogravure type varnishes and inkscontaining a solution oi a polybasic acid in a solvent: heat set typeinks and varnishes which are acidic (neutral resins are preferably madeacidic by reaction with an olefin polycarboxylic anhydride and thentreated in accordance with the invention). I

In order to illustrate and point out some of the advantages of theinvention. but in no sense as a limitation thereof as otheiwhe disclosedherein, the following specific examples are included.

Example 1 500 grams of a commercial acidic resin sold under the tradename "Teglac 127", the preparation of which is described in U. 8. PatentNo. 2,063,542 by a reaction of glycerol, rosin and a iumaric or maieicacid or derivative thereof, was dissolved in 750 grams of toluol. 20grams of tetraethylene pentamine was added. A small amount ofprecipitate formed. The whole reaction mass was freed of'solvent bydrying in a vacuum oven. The resulting solid was pulverized and 200grams dissolved in 300 grams of diethylene glycol. The resulting varnishhad a higher viscosity than a corresponding composition containing nopolyamine.

Example 2 20 grams of commercial dry calcium'lithol was ground in 80grams of polyamine varnish composition oi? Example 1 on a conventionalthree roller mill. The pigment was thoroughly wetted and the milledcomposition possessed good body and good flowing characteristics.

In a corresponding run using 20 grams of the same dry color and acorresponding amount of the corresponding polyamine free varnish asdiscussed in Example 1, the body and flow characteristics of the productobtained were poorer than the above polyamine salt product.

Example 3 parts by weight of a commercial acidic resin sold under thetrade name Teglac 12?" (described in Example 1) was dissolved in 50parts by weight of hexaethylene glycol and then 30 parts by weight ofcommercial iron Example 4 500 parts by weight of a commercial acidicresin sold under the trade name Teglac 127 (described in Example 1) wasdissolved in 500 parts by weight of the acetate of the monobutyl etherof diethylene glycol, and 10 parts by weight of tetraethylene pentaminewas dissolved therein. In 850 parts by weight of the resulting varnishwas flushed 2075 parts by weight of an aqueous suspension of acommercial highly resinated calcium lithol containing 19.2% by weightsolids. The mixture was allowed to stand, and an upper water layerformed. This water was decanted from the pasty lower layer. The moistpaste was vacuum dried. The dried paste was mixed with 298 parts byweight of diethylene glycol and 4 parts by weight of tetraethylenepentamine. The resulting product possessed good body and flowcharacteristics, and a clear and transparent print tone and mass tone,

8 g trample scribed in Example I) was dissolved in 50 Darts am hi; 1 byweight or diethylene glycol: and 2 parts by 08 g by 2,2 5 f g ggg figmg'g weight oi hepta-ethanol-tetra-ethylene-pentab weight of ethylenediamine was dissolved there- 1 in. Several inks made b rindin usual 1ments in this varnish and ad ding usual dilu nis ting characteristicsthan cud the rnishes showed better body. flow and viscous stabilitycharacteristics than the corresponding polyamine f mks 1 ms 1 suitablefor moisture or steam-set printing "ink m wh ch were othe e s mflarlymade 15 purposes. They all showed sumcient moisture Example 6 toleranceto give good press life in the standard 715 parts by weight f methanolamine and printing press rooms under the various humidity 1500 parts byweight of ethylene glycol were conditmns mixed and heated to 50 0., then747.5 parts by Example 10 weight of refined shellac was added thereto 92parts by weight of a terpene resin modified tamed at between and Then373 type phenolic resin this having the following parts of diethyleneglycol mono ethyl ether physical pmpemes:

(Carbitol) was added, followed by 165.75 parts o o o by weight oftriethanol amine, and finally 214.5 Melting mm 3 3%. $553,, parts byweight oi'water was added. In 80 parts V tube me'thod) by weight of theshellac solution, was ground 20 color w rosin scale parts by weight ofcommercial calcium lithol Acid numb;r 5M0 pigment (the calcium salt Orthe reaction product Refracflve index t 250 c of diazotized2-nabhthylamine4-sulfonic acid specific gravity at 25 c 1 0 5 andbetanaphthol), using a three roller mill. weight per 934 Alterdispersion was complete, 5 parts by wei ht Bulking 11b bu|ks 1102ga1printing ink obtained therefrom, by adding 414 parts by weight of highmelting Poin es r usual diluents, showed better body, flow and s m. 312parts by weight of a rosin modified viscous stability characteristicsthan correspondpe phenolic resin. this resin having the followingurea-free inks which were otherwise similarly in: proflcrtiesr made.

mm 7 fiiiffifffff:::::::::::::::::::::::::ii parts by weight of anacidic resin prepared M. P. c 142-149 by reacting one or more terpeneswith maleic or Acid No .12-l8 fumeric acid or derivatives thereof instoichiomeme proportions and having a s ft ing point 7 and 2208 parts byweight of stand oil were mixed oi 40-50 C. and an acid number of about530, 45 and heated to with agitation; 37 parts is dissolved in 40 partsby weight of diethyle e by weight of lead acetate and 37 parttls byweight poly action mass was cooled to 100 0. 34' parts by H 4 amine-freeinks which are otherwise similarly Weight of tetmethylene Pentamme wasadded ad and mixed therein.

Emm 1e 8 The resultin p ype dryin oi ethylene-pentamine, the purematerial may be Example 1! Wm 567 parts by weight of a partial glycerideof (Howl-141m (CflHiNCIHiOH) 01340?! 06 .the adduct of main and maleicanhydride, ob-

body and flow characteristics than correspondparts by weight or amineral oil traction boiling l inc-free inks which were otherwise in therange 265 to 300 0-, and 8.5 parts y mg mde. weight of commercialhepta-ethyl-tetra-ethy- 50 parts by weight of a commercial acidic resinThe resulting produ was an excellent vehicle sold under the trade name"'I'eglac 127 (defor heat set types 01' printing ink.

Example 12 183 grams oi polymerized wood grams oi dehydrated castor oiland i450 oi stand oil were mixed, agitation at 290 C. until theviscosity oi the reaction mass was approximately 20 poises at 25 0.;then the reaction was checked by the addition oi 534 g. of the rosin. Itwas cooled to 100 C., and 22 grams oi tetra-ethylene-pentamine was mixedtherein,

Several inks were prepared by grin dry colors therein and diluting withthe. usual diluents. Each oi these non-gloss inks showed better body,now, pigment wetting and strength characteristics than correspondingtree inks which were similarly the presence Several prin made except torthe polyamine component.

Example v13 83 parts by weight oi polymerized wood rosin, 183 parts byweight oi dehydrated castor oil and 14 0 par s by weight oi aged linseedoil were mixed, and thenheated with agitation at 295-300 0. until theviscosity oi the reaction mass was approximately poises at C. Thereaction was then checked by the addition oi 534 parts oi the woodrosin. It was cooled to 100' C. and 22.5 parts by weight oitetra-ethylene-pentamine was mixed therein.

Several inks were prepared by mixing usual colors in the above productas a vehicle (including milori blue, resinated lithol, and monastrolblue). Each oi these showed better pigment wetting characteristics thandid corresponding polyamine-iree links which were prepared similarlyexcept ior the presence oi he polyamine component. .The body and flowcharacteristics oi theiormer were also better than those oi the latter.Printed sheets made thereirom showed cleaner print, less bronze, andhigher gloss characteristics ior the iormer than for the latter.

Example 14 20 parts by weight oi ester gum, 20 parts by weight oi apartial glyceride oi a rosin-maleic anhydride adduct (described inExample ii) and 40 parts by weight oi isopropyl acetate were mixed; then0.8 parts by weight 0! tri-ethylenetetramine was mixed therein. Theresulting varnish was an excellent rotogravure ink vehicle.

Several rotogravure were prepared by mixing usual pigments in the abovevehicle. Each oi these showed better pigment wetting characteristicsthan did corresponding polyamlne-iree which were prepared similarlyexcept for the presence of the polyamine. Similar improvements werobserved in the body, now 8228 print characteristics oi the polyaminesalt 1 Ezample 15 parts by weight oi a partial glyceride oi oi resin andmaleic anhydride obreacting the acidic resin described glycerol to givea value of was dissolved in 450 parts by weight oi isopropyl acetate.when the resin was completely in solution, there was added 10 parts byweis lit 0! commerpolyamineresin selected polyamine Example 16 500 partsby weight oi a rosin modified phenolic resin, described in Example 10,were in 550 parts oil traction boiling in the range 0! 2 by weight oicommercial N-lauryl tetraethylene pentamine were added to the resinsolution and stirred in. This vehicle, especially adapted in: heat settypes oi printing inks. was iound to possess a pigment wettingproperties and to give color dispersions oi good flow.

Although a number oi examples oi compounding resinous compositionsaccording to the invention have been given herein, it to be understoodthat the invention or thereby, but is susceptible oi changes in term anddetail within the scope oi th claims.

The term composition consisting essentially of" appearing in theiollowing claims ited to compositions consisting exclusively specifiedessential ingredients, those containing other added ingredl do notdeieat the purpose oi the invention, in accordance with the disclosure 1claim:

1. A composition consisting essentially oi a substantially amide-treepolyamine salt of an acidic from the group consisting oi acidicsynthetic and acidic modified neutral resins in a polyglycol.

2. A composition consisting essentially oi a substantially amide-freepolyamine salt oi an acidic selected irom the group consisting oi acidicdined neutral resins in a polyethylene glycol.

3. A composition consisting essentially of a su stantially amide-treepolyamine salt oi an acidic resin selected from the group consisting oiacidic synthetic and acidic modified neutral resins in a diethyleneglycol.

4. A composition consisting essentially of a pigment and a substantiallyamide-free polyethylene polyamine salt of an acidic alkyd resin solublein a glycol solven 5. A composition consisting essentially of a pigmentand a substantially amide-free polyethylene polyamine salt of arosin-ethylene dicarboxylic acid derivative adduct soluble in a glycolsolvent.

6. A composition consisting essentially oi a pigment and a polyaminesalt oi a terpene ethylene acid derivative adduct soluble in a glycolsolvent.

7. A composition consisting essentially oi a pigment and a substantiallyamide-free polyethylene salt oi an acidic alkyd resin soluble in apolyethylene glycol.

8. A composition consisting essentially oi a pigment and a substantiallyamide-free polyamine salt of a rosi -ethyiene dicarboxylic acidderivative adduct soluble in a polyethylene glycol.

9. A com sition consisting essentially oi a pigment and a substantiallyamide-tree polyethylene lyamine salt oi a terpene ethylene dicarboxylicacid derivative adduct soluble in a polyethylene glycol.

10. A composition consisting essentially pigment and a substantiallyamide-tree o! a p yethylene polyamine salt of an acidic alkyd resinsoluble in diethylene glycol.

11. A composition consisting essentially of a pigment and asubstantially amide-free polyethylene polyamine salt of a rosin-ethylenedlcarboxylic acid derivative adduct soluble in diethylene glycol.

12. A composition consisting essentially of a pigment and asubstantially amide-free polyethylene polyamine salt of a terpeneethylene dicarboxylic acid derivative adduct soluble in diethyleneglycol.

13. The method of stabilizing a printing ink vehicle composedessentially of a solution of an acidic resin in a solvent therefor,which consists in treating the solution with a polyamine capable of atleast partially converting said acidic resin in solution into apolyamine salt of said resin, whereby a polyamine salt of the acidicresin is formed therein.

14. The method of stabilizing a printing ink vehicle composedessentially of a dispersion of an acidic resin in a drying oil, whichconsists in treating said vehicle with a polyamine capable of at leastpartially converting said acidic resin into a polyamine salt of saidresin, whereby a polyamine salt of the acidic resin is formed therein.

15. The method of stabilizing a printing ink composed essentially of apigment dispersed in a solution of an acidic resin in a solvent thereforwhich consists in treating the ink with a polyamine capable of at leastpartially converting said REFERENCES CITED The following references areof record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,111,802 Oswald Mar, 22, 19382,304,369 Morgan et a] Dec. 8, 1942 2,309,088 Auer Jan. 26, 19432,312,732 Salathiel Mar. 2, 1943 2,356,025 Bergaminl Aug. 15, 19442,371,212 Bassford et a1 Mar. 13, 1945 2,382,838 Weber Aug. 14, 19452,387,049 Bassford Oct. 16, 1945 OTHER REFERENCES "Glycerol and theGlycols," by Lawrie (1928), pages 381-385 inclusive.

